CN1134472A - Process for production of pure solutions of tungsten and molybdenum - Google Patents
Process for production of pure solutions of tungsten and molybdenum Download PDFInfo
- Publication number
- CN1134472A CN1134472A CN96101517A CN96101517A CN1134472A CN 1134472 A CN1134472 A CN 1134472A CN 96101517 A CN96101517 A CN 96101517A CN 96101517 A CN96101517 A CN 96101517A CN 1134472 A CN1134472 A CN 1134472A
- Authority
- CN
- China
- Prior art keywords
- solution
- molybdenum
- aluminium
- arsenic
- phosphorus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 19
- 239000010937 tungsten Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 11
- 239000011733 molybdenum Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 14
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000010955 niobium Substances 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011135 tin Substances 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000005349 anion exchange Methods 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 5
- 238000002309 gasification Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- -1 Alkali metal salt Chemical class 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/18—Alkaline earth metal compounds or magnesium compounds
- C25B1/20—Hydroxides
Abstract
Process for the production of pure tungsten and/or molybdenum solutions from sources, such as alkaline decomposition solutions, which are contaminated with tantalum, niobium, titanium, aluminium, tin, arsenic, phosphorus and/or silicon, by application of a three stage purification process of pH reduction, anion exchange and membrane electrolysis.
Description
The present invention relates to be subjected to the pure tungsten of tantalum, niobium, titanium, aluminium, tin, arsenic, phosphorus and silicon pollution and/or the method that the molybdenum decomposing solutionization prepares pure tungsten and/or molybdenum solution.
Alkali metal salt soln can be by making from the starting material such as tungstenic such as ore, chip, recycled materials and/or molybdenum such as various caustic leaching processes such as pressurization lixiviate, calcining or fusing decomposition.With raw-material difference, the alkaline solution of these pH values 13 to 14 can be by tantalum, niobium, titanium, tin, arsenic, phosphorus, silicon and/or aluminum pollution.
These pollutents are precipitated out by adding mineral acid reduction pH value to 8 and 10 so far, and arsenic and phosphorus also are precipitated out by adding magnesium and/or aluminium salt.
According to the European patent application EP-A219787 that has delivered, reduce pH and also can select for use so-called electrolysis to fall acidization.But owing to be present in the former solid of pollutent in the decomposed solution, particularly in serious contaminated solution, in the film electrolysis meeting described in the document since on anode sedimental formation and film go wrong owing to throw out and sedimental obstruction.
The system point that has the neutral salt that to handle a large amount of generations when operation is finished with inorganic acid for adjusting pH.
In any case, phosphorus, arsenic and silicon are precipitated out by adding magnesium and/or aluminium salt even be about at 9 o'clock at pH, also can produce other salt and increased the weight of the lifting capacity of abraum salt in the waste water.In addition, arsenic can not be finished and obtain separating.
Therefore the purpose of this invention is to provide specifically by tantalum, niobium, titanium, tin, arsenic, phosphorus and the alkaline molybdenum of silicon pollution and/or the purification process of tungsten decomposing solution.Thereby another object of the present invention is to handle this solution to prepare pure molybdenum and/or tungsten solution under the situation that does not add exogenous salt and mineral acid.
According to the present invention, found to carry out continuously the mode of the environmental sound of three treatment steps, this method can prepare pure tungsten and molybdenum compound from alkaline decomposing solution, and described compound is suitable for isolating pure metal and/or metallic compound as starting material.
-the first step is by importing CO
2Gas reduces pH,
-the second step, carry out that anionresin is handled and
In three steps of-Di, carry out the film electrolysis.
Therefore the invention provides the three-step approach for preparing pure tungsten and/or molybdenum solution from the alkaline decomposing solution that is polluted by tantalum, niobium, titanium, tin, arsenic, phosphorus and silicon.The first step is with CO
2Gas charges into described alkaline decomposing solution and reaches 8 to 10 until the pH of solution, and wherein element tantalum, niobium, aluminium, titanium and tin have obtained partly separating.In second step, at pH6 to 10 top remaining pollutent and arsenic, phosphorus and silicon are got rid of together fully with anionite.In the 3rd step, the solution of purifying is further handled by the film electrolysis of cation selective film, and wherein NaOH reclaims at cathode terminal, CO
2Gas reclaims at positive terminal.
For example in order to isolate the pure wolframic acid or the ammonium salt of molybdic acid, and then the third step of described method preferably carries out the further aftertreatment of described metal salt solution by solvent extraction.
Eliminate or greatly reduced neutral salt Na according to method of the present invention
2SO
4, NaCl generation, and can be used to decompose raw-material NaOH and the required CO of neutralization
2Recycled therein.
CO in the first step
2In gasification and the preprocessing process, alkali decomposes the alkali metal salt soln CO that produces
2Gasification reaches between 8 to 10 the pH value.In this pH scope, element aluminum, tin, silicon, tantalum, niobium and titanium partly are precipitated out and can pass through filtering separation.
In ion-exchange purification subsequently, remaining pollutent arsenic, phosphorus and silicon and remaining above-mentioned element are separated from filtrate below pH8 in addition more in large quantities with weak base anion exchanger.Pollutent arsenic, phosphorus and silicon can be so basically fully from for example separating the tungsten solution.Therefore this separation is significantly than coming sedimentary method more effective with adding magnesium or aluminium.
In film electrolysis acidifying subsequently, the solution of having removed tantalum, niobium, titanium, tin, arsenic, phosphorus, aluminium and silicon can be acidified to tart pH scope by the film electrolysis.At the concrete cation selective film that uses of this stage.
Sodium hydroxide solution can reclaim well and can reuse in decomposing the raw material process at cathode terminal.
Owing to obtain below 7 in positive terminal pH value, so CO
2Can reclaim and recycle again at this.
The back purifying that extracts by solution is selective row as required, wherein thisly can further handle with known method through prepurification and acidifying solution, as if ion exchange method (by solvent extraction or use solid ion-exchange resin), or produce pure former material pump to prepare metal or metallic compound by precipitation.
To situation of the present invention be described by non-limiting example below.
Embodiment
Step 1 CO
2Gasification, pre-neutralization
After being diluted to about 2 times of volumes, the alkaline tungsten solution with water that decomposition is closed in the fusing of Wimet residue that contains the Ti of the Ta of Nb, 73mg/l of Al, 88mg/l of W, 160mg/l of 156g/l and 42mg/l passes to CO by the agglomerating sheet glass
2Gas vaporization is to pH8.2.Form the small amount of precipitate thing of being made up of Al, Ti, Ta, Nb and Si basically when gasification, solution still contains the tungsten of about 15 (weight) %.
Step 2
A. ion-exchange aftertreatment
In step subsequently, use CO
2Pre-neutralization also contains the exchange resin [the LEWATIT MP62 of Bayer AG (OH ionic)] of filtrate by the 300ml weak base anion exchanger is housed of about 70g/l tungsten and residual contamination thing.Crossed and obtained about 4 liters solution behind the exchange column.The concentration of this tungstenic liquid be 65g/l and basically eliminate all contaminants make it reduce to the level of trace.
B. from the Circulation of the tungsten of filtrate
Then with sodium hydroxide solution wash-out anionite and make it get back to the OH attitude.This strong basicity elutriant (about 1 liter) also contains the tungsten of about 55g/l solubilised state except the pollutent that contains the fundamental quantity that imports with described decomposing solution.This waste liquid is passed to sub-fraction CO
2Gas after sedimentary pollutent filtering, turns back to step 1 with it, the tungsten of being carried secretly with recovery in the preceding loop.
The acidifying of step 3 tungsten solution, the film electrolysis
Cross membrane electrolytic cell (mould material: Nafion 90209, DuPont produces) through the solution stream of step 2 purifying.When initial cell voltage is 4.6v, obtain the strength of current (current density: 0.4A/cm of 20A
2).After 8 hours, be under the situation of 8V, reached and be about 2 pH value that electrolysis simultaneously stops at the last voltage of anode.In this experimental scale, do not collect gaseous state CO
2The release air-flow, it is not returned because of step 1, although these continuous operations to this method are feasible and rational yet.
The concentration that obtains on negative electrode is about the sodium hydroxide solution of 100g/l, and it can be used for wash-out and anion regenerant exchanger or is used for the lixiviate starting material in the implementation and operation.
The further processing of this purified solution:
Carrying out solvent extraction with the method for knowing with secondary amine then separates very pure ammonium paratungstate from described acid tungstate solution.The branch folding result of final product shows that the content of pollutent in the product that contains 69.5% tungsten is: Al＜3ppm, As:＜5ppm, Ca:＜3ppm, Co:＜2ppm, Cu:＜1ppm, P:＜5ppm, Si:＜10ppm, K:＜1ppm, V:＜1ppm, Fe:6ppm, Na:2ppm.
Claims (3)
1. prepare the three-step approach of pure tungsten and/or molybdenum solution from the alkaline decomposing solution that is polluted by one or more materials tantalum, niobium, titanium, tin, arsenic, aluminium, phosphorus, the silicon, it is characterized in that:
(a) the first step: described alkaline decomposing solution is filled with CO
2Gas reaches 8 to 10 scopes up to the pH of solution, thereby element tantalum, niobium, aluminium, titanium and tin are partly separated,
(b) second the step: with above-mentioned residual pollutent and arsenic, aluminium, phosphorus and silicon are disposed under pH6 to 10 scope fully with anionite and
(c) the 3rd step: purified solution is further handled by the film electrolysis of cation selective film, thereby reclaimed NaOH, reclaim CO at its positive terminal at its cathode terminal
2Gas.
2. the method for claim 1 is characterized in that described metal salt solution carries out the back purifying by solvent extraction in further (the 4th goes on foot) handles.
3. the method for preparing tungstenic and/or molybdenum solution, comprise: the pH of alkaline decomposing solution is transferred to 8 to 10 scope, this solution is carried out anionresin handle under the situation of pH6 to 10, carry out the film electrolysis with the cation selective film then, when regulating pH, do not add mineral acid or inorganic salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19500057A DE19500057C1 (en) | 1995-01-03 | 1995-01-03 | Environmentally friendly prodn. of pure tungstate and molybdate soln. |
| DE19500057.9 | 1995-01-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1134472A true CN1134472A (en) | 1996-10-30 |
| CN1060819C CN1060819C (en) | 2001-01-17 |
Family
ID=7750949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96101517A Expired - Fee Related CN1060819C (en) | 1995-01-03 | 1996-01-03 | Process for production of pure solutions of tungsten and molybdenum |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5676817A (en) |
| EP (1) | EP0721017B1 (en) |
| JP (1) | JPH08231225A (en) |
| KR (1) | KR960029490A (en) |
| CN (1) | CN1060819C (en) |
| AT (1) | ATE178361T1 (en) |
| AU (1) | AU693961B2 (en) |
| CA (1) | CA2166368A1 (en) |
| DE (2) | DE19500057C1 (en) |
| HU (1) | HU213647B (en) |
| RU (1) | RU2144572C1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167401A (en) * | 2011-03-14 | 2011-08-31 | 崇义章源钨业股份有限公司 | Method for dephosphorizing aluminum tungstate ((NH4)2WO4) solution |
| CN104678778A (en) * | 2013-11-08 | 2015-06-03 | 洛克威尔自动控制技术股份有限公司 | Time synchronization of signal transmission intervals for simulating a machine in industrial automation |
| CN106350848A (en) * | 2016-09-19 | 2017-01-25 | 上海应用技术大学 | Method for preparing nanometer material by depositing molybdate on carbon fiber surface |
| CN116495784A (en) * | 2023-06-20 | 2023-07-28 | 赣州市海龙钨钼有限公司 | Method for purifying ammonium paratungstate in ammonium tungstate solution |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19724183C2 (en) * | 1996-07-05 | 1999-03-25 | Starck H C Gmbh Co Kg | Process for the preparation of pure alkali and / or ammonium tungstate solutions |
| DE10341727A1 (en) * | 2003-09-10 | 2005-04-28 | Starck H C Gmbh | Purification of ammonium metalate solutions |
| JP5662690B2 (en) * | 2010-03-05 | 2015-02-04 | 国立大学法人名古屋大学 | Method for producing ammonium tungstate aqueous solution |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3947332A (en) * | 1974-06-07 | 1976-03-30 | Gte Sylvania Incorporated | Preparation of heteropoly acids of tungsten and molybdenum |
| ZW2786A1 (en) * | 1985-02-14 | 1986-05-14 | Anglo Amer Corp South Africa | Removal of sodium ions from alkaline aqueous solutions by means of an electrolytic membrane process |
| HU203132B (en) * | 1985-10-15 | 1991-05-28 | Mta Mueszaki Fiz Kutato Inteze | Process for producing purified volfram and/or molybden isopolyacids or salts from impure alkalic volfram and/or molybden metal-salt solutions |
| US4975167A (en) * | 1985-10-15 | 1990-12-04 | Mta Kozponti Fizikai Kutato Intezete | Process for production of pure tungstic acid or molybdic acid from impure alkali metal tungstate or molybdate solutions |
| EP0389661B1 (en) * | 1989-03-31 | 1993-11-10 | Walhalla-Kalk Entwicklungs- und Vertriebsgesellschaft mbH | Process for removing arsenic from waste waters |
| RU1836466C (en) * | 1992-04-07 | 1993-08-23 | Всероссийский научно-исследовательский и проектный институт тугоплавких металлов и твердых сплавов | Method of tungsten concentrates processing |
-
1995
- 1995-01-03 DE DE19500057A patent/DE19500057C1/en not_active Expired - Fee Related
- 1995-12-21 EP EP95120316A patent/EP0721017B1/en not_active Expired - Lifetime
- 1995-12-21 AT AT95120316T patent/ATE178361T1/en not_active IP Right Cessation
- 1995-12-21 DE DE59505509T patent/DE59505509D1/en not_active Expired - Fee Related
- 1995-12-22 US US08/577,255 patent/US5676817A/en not_active Expired - Fee Related
- 1995-12-27 JP JP7351215A patent/JPH08231225A/en not_active Ceased
- 1995-12-28 AU AU40680/95A patent/AU693961B2/en not_active Ceased
- 1995-12-29 HU HU9503921A patent/HU213647B/en not_active IP Right Cessation
- 1995-12-29 KR KR1019950067688A patent/KR960029490A/en active IP Right Grant
- 1995-12-29 CA CA002166368A patent/CA2166368A1/en not_active Abandoned
-
1996
- 1996-01-03 RU RU96100066A patent/RU2144572C1/en active
- 1996-01-03 CN CN96101517A patent/CN1060819C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167401A (en) * | 2011-03-14 | 2011-08-31 | 崇义章源钨业股份有限公司 | Method for dephosphorizing aluminum tungstate ((NH4)2WO4) solution |
| CN104678778A (en) * | 2013-11-08 | 2015-06-03 | 洛克威尔自动控制技术股份有限公司 | Time synchronization of signal transmission intervals for simulating a machine in industrial automation |
| CN106350848A (en) * | 2016-09-19 | 2017-01-25 | 上海应用技术大学 | Method for preparing nanometer material by depositing molybdate on carbon fiber surface |
| CN106350848B (en) * | 2016-09-19 | 2018-08-03 | 上海应用技术大学 | A kind of preparation method of carbon fiber surface deposition molybdate nano material |
| CN116495784A (en) * | 2023-06-20 | 2023-07-28 | 赣州市海龙钨钼有限公司 | Method for purifying ammonium paratungstate in ammonium tungstate solution |
| CN116495784B (en) * | 2023-06-20 | 2023-09-15 | 赣州市海龙钨钼有限公司 | Method for purifying ammonium paratungstate in ammonium tungstate solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2166368A1 (en) | 1996-07-04 |
| HU213647B (en) | 1997-09-29 |
| AU693961B2 (en) | 1998-07-09 |
| CN1060819C (en) | 2001-01-17 |
| DE19500057C1 (en) | 1996-02-29 |
| EP0721017A1 (en) | 1996-07-10 |
| RU2144572C1 (en) | 2000-01-20 |
| JPH08231225A (en) | 1996-09-10 |
| EP0721017B1 (en) | 1999-03-31 |
| HUT74111A (en) | 1996-11-28 |
| US5676817A (en) | 1997-10-14 |
| HU9503921D0 (en) | 1996-05-28 |
| KR960029490A (en) | 1996-08-17 |
| ATE178361T1 (en) | 1999-04-15 |
| AU4068095A (en) | 1996-07-11 |
| DE59505509D1 (en) | 1999-05-06 |
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